Hydroxypentachlorodimethoxymethanotetrahydroindane



Patented Oct. 7, 152

'intuitor nzmN'rAcHLononnvrn'rHoXY- I=:METHANOTETRAHYDROINDANE ;,l Ili'Croxall Bryn Athyn P a.,and'John 'W.

Dawson, Huntsvllle Ala assignors' to Bohm &

Haas Company;PhiladelphiaiPa a corporation .ofDelaware o No Drawing. Application pecemberiiil iifib,

Serial No. 200,085; 4 1 Claim. (c1. 359L 1 This invention deals with 2-hydroXy-l,4,5,6,7- org nj'i'csblventboiling-from abontso -c.td iso pentachloro 8,8 dimethoxy 4,7 methanoq lsuch as benzene; toluene, xylene, or naphtha:

30,4 7,?a tetrahydroindane andwith fa method Itis", desirable} to have present in the reaction for' itsfpr'eparatioh. w H r l mixture at polymerization inhibitor, such as "Ir'i four'applicationSerial No. 1'0 0,'76 6,"filed' June 5' h'ydroqiiinon'e ,or naphthol, "an amount of "in-' 22 1949, now U. S'J'Patent No. 2,562,893, issued" hibitor fijom 0.01% to 5% of the weight of react? August '7 1951', of whichthe presentapplication antsbein'g suitable. The reacti'on mixture is is a continuation-impart, itfis shownthat'h'exa stirred, and heatedat50iC; tdlOOfyCfiandthn chlorocyclopentadienefl reacts 'with an] alcohol; separated by distillation. The productistetr'a ROH, in'the presence oi astrongfalkaH-to form 1 ichlorodin iethoxymethanotetrahydroindene.'.

1,1 1- .dialkoxy 2,33,5 tet'rachlorocyclopentadij This 'isreacted with hypochlorous acidjf'The ene and thatflthi's dialkoxy compound reacts by reaction is eiiectedfby stirring together afsolu-l adding to cyclopentadiene to form 4,5,6,7-tetration of the above, product in an organic'solvent' chloro 4,7 methano 8,8 dialkoxy 3a,4,7,7awith an aqueous solution containing from. about" tetrahydroindene. In the above formula R is a 2% to 7% or hypochlorous'acid.' The'niixtureis monovalent' hydrocarbon group, @particularly a warmed to' promo'tethe reaction and continued non-tertiary alkyl group of notovereight carbon until, the reaction is reasonably. complete. The atoms. In our above-identified application tetraorganic layer is then separated, washed with chloromethanodialkoxytetrahydroindene is. rewater, and distilled. actedwith chlorine to.form hexachloromethan'o A typical preparation follows." Parts; shown dialkoxytetrahydroindane; whiclris a pot'ent'inaid-byweight. o U i U secticidal'agent'ag'ainst flies',"roach'es, andvariou's If if: I; other insects.

We have now found that when 4,5,6,'7-tetra- (a) Potassium hydroxide in an amount of chloro 4,7 methano 8,8-dimethoxy-3a,4,7,7a- 123.5 parts (2.2 moles) is dissolved in 256 parts tetrahydroindene is reacted with an aqueous (8 moles) of methanol and the solution added. solution of hypochlorous acid between about 25 Slowly er three h u s to a Well-Stirred p C. and 75 0., there is formed the Z-hydroxysion of 272.5 parts (1.0 mole) of hexachlorocyclopentachloro indane derivative. While this new Pentadiehe in 126 parts (4.0 moles) of methanol compound resembles our hexachloro compound 3 at 5 C.-10 C. After addition is comple he in some respects it possesses, rather surprisingly, reaction mixture is allowed to come t0 room temproperties not exhibited by the hexachloro com- Derature Wh l b in Stirred over four hours. pound Furthermore, through th hydroxyl Stirring is continued overnight. The reaction group of t compound of t invention there mixture is brought to neutrality by the addition are formed acyl derivatives by reaction with carhy r hloric acid and filtered. The boxylic anhydrides or acid halides or phosphites Potassium Chloride Separated s Washed with or phosphates by reaction with phosphorus oomacetone and the washings added to the filtrate. pounds such as phosphorous chloride or bromide, The liquors are S pp d of solvent and distilled phosphorous sulfides. phosphoryl halides such as in vacuo to give a 90% yield of Llim ydiethylphosphoryl chloride, etc. The compound .5-tetra l rocy l p distilling at of this invention is thus a valuable chemical This product has fractive i t t index, n of 1.5282, and contains 53.88% of For the preparation of this compound there 0111011118 (theory may be taken as a starting material hexachloro- (b) There are dissolved 264 parts ole) of cyclopentadiene. This is reacted between 0 C. t Compound and 2 p r i iaphthol and 60 C. with methyl alcohol, usually in excess, i 2 0 parts of toluene and the mixture is heated in the presence of about two molar proportions to reflux pe u S ty-six p s (1.0 mole) of an amali hydroxide per 1 of hexachlorm of cyclopentadiene are introduced below the surcyolopentadiene, Any excess lk is t p face over four hours to the well-stirred, refluxing ized and the dimethoxytetrachlorocyclopentadi- 31119116 50111151011- Stirring and h ing are conene formed is separated by tm n t 1 tinued for 30 minutes. The reaction mixture is pressure. A similar reaction can be effected with Stripped f Solve and distilled in vacuo giving th l h l a 75% yield of 4,5,6,7-tetrachloro-4,7-endo- The above dimethoxy compound is reacted methylene 8,8 dialkoxy 3a,4,7,'7a tetrahywith cyclopentadiene, conveniently in an inert droindene distilling at 114 C./0.5 mm.

oil and replaced with a second portion of 1000" parts of the hypochlorite solution and the mixture stirred with warming. This was repeated twice again with 1000-part portions of hypochlorous acid solution.

The whole operation required six hours. The organic layer was then 1 thoroughly washed with water, stripped of solvent, and distilled at low pressure. After a forerun of 34 parts up to 170 C./2.5 mm., there was taken a fraction at 168 C./1.5 mm. to 174/ C.1 mm. which had a refractive index at 20 C. of 1.5540. Another fraction was then taken between 168 C./1 mm. and 188 C./1.5 mm. which had a refractive index of 1.5550. Both fractions proved to be essentially a compound corresponding in composition to 2hydroxy-1,4,5.6,7-pentac'hloro-8,8-dimethoxy 4,7 methane 7 3a,4,7,7atetrahydroindane or tothe isomer in which hydroxyl group and chlorine atom are interchanged. Analyses showed a carbon content of 37.7% and a hydrogen content of 3.2% (theory 37.7%andl 3.4% respectively).

This compound was mixed with a finely divided solid diluent or carrier and a wetting agent to give a wettable powder. The powder was tested against armyworm at 1:100, giving an 80% kill.

A 2 solution was made in deodorized kerosene. It was applied against roaches. A one cc. dose under standard test conditions gave a 100% kill and a 0.6 cc. dose a 70% kill. A one cc. dose of a 1% solution gave a 92% kill and of a 0.5% solution a 90% kill.

While a 2% solution in kerosene did not give knockdown in the Feet-Grady test, a'combination spray containing 2% of the above compound and pared aboveii's:

4 1% of butoxyethoxyethyl thiocyanate gave a knockdown of 96% and a kill of +55 compared to the Oflicial Test Insecticide.

A self-emulsifiable composition was prepared from one part of the above compound. two parts of aromaticsolvent, and one part of afnon-ionic emulsifier; This was used in a spray in water at a dilution of 1:400, 1:800, and 1:1600 (on the basis of the compound). Kills of aphids were. 94%, 91%;, and 93% respectively. These tests and others-demonstrate that the above compound is a very effective aphicide.

The probablejstructure of the compound pre- H ROOOR y We claim:

I REFERENCES CITED The following references are of record in the file of this patent:

' UNITED STATES PATENTS Number I Y Name Date 2,562,893 Dawson. et al. (I) Aug. 7,'1951 2,588,215 Dawson et a1. (ID Mar. 4, 1952 

